O-ethyl-S-n-butyl-O-(2- or 3-nitrophenyl) phosphorothiolates

ABSTRACT

Nitrophenylthiolphosphoric esters of the formula ##STR1## wherein R 1  represents methyl or ethyl, 
     R 2  represents propyl or butyl, and 
     R 3  represents hydrogen, methyl or chlorine, 
     Processes for their manufacture and their use in pest control a novel composition of reduced mammaliam toxicity.

The present invention relates to nitrophenylthiolphosphoric esters,processes for their manufacture and their use in pest control.

The nitrophenylthiolphosphoric esters have the formula ##STR2## whereinR₁ represents methyl or ethyl, R₂ represents propyl or butyl prefereablyn-propyl, and R₃ represents hydrogen, methyl or chlorine.

Therefore the formula I claims compounds, wherein R₁ represents methylor ethyl, R₂ represents n-propyl, and R₃ represents hydrogen, methyl orchlorine, or wherein

R₁ represents methyl or ethyl,

R₂ represents n-butyl and primary i-butyl,

R₃ represents hydrogen, methyl or chlorine.

This invention relates to the unusual properties of certain O,S'-dialkylnitrophenyl thiophosphates and phenyl substituted derivatives thereof.O,O'-Dimethyl and diethyl nitrophenyl thiophosphate esters are widelyknown insecticides. Certain compounds of this type are extensively usedfor insect control, e.g. Parathion, Methyl-Parathion, Sumithion,Chlorthion, Dicapthon. Their synthesis and insecticidal action isdescribed in the first volume of a monograph entitled "Chemie derPflanzenschutzund Schadlingsbekampfungsmittel", edited by R. Wegler,published by Springer Verlag, New York, 1970; on pages 306 to 311. Theapplication of such insecticides is often limited because of their hightoxicity to warm-blooded animals. The search is therefore continuing tofind novel thiophosphates of superior pesticidal effectiveness and atthe same time reduced toxicity.

In the present invention it was found that the toxicity of such esterscan be unexpectedly reduced and/or their pesticidal effectivenessmaintained or suprisingly broadened by a structural isomerizationinvolving the conversion of thiono sulfur to thiolo sulfur. For example,isomerized compositions were found to have fungicidal activity.Furthermore, it is surprisingly found that for the optimization ofproperties, the novel isomerized compositions should possess and O-ethylgroup and an S-C₃ to C₄ alkyl group. An n-propyl or primary i-butylgroup is a uniquely suitable substituent for the sulfur. These novelS-substituents were completely unsuitable in the known, O,O-dialkylthiophosphate esters.

The structural change from the known to novel esters is exemplified bythe following scheme: ##STR3## wherein R₃ is hydrogen, methyl orchlorine.

The novel compounds of the formula I can be manufactured by thefollowing methods: ##STR4##

In the fromulae, R₁, R₂ and R₃ have the meanings given for the formulaI, Me represents an alkali metal, in particular sodium or potassium, orthe group (R₄)₃ -NH⁺, wherein R₄ represents hydrogen or alkyl, R₅represents an alkyl radical and Hal represents a halogen atom, such aschlorine, bromine or iodine.

Suitable acid binding agents are: tertiary amines, e.g. trialkylamines,pyridine, pyridine bases, dialkyl anilines; inorganic bases, such ashydrides, hydroxides; carbonates and bicarbonates of alkali and alkalineearth metals. During the reactions it is sometimes necessary to use acatalyst, e.g. copper or copper chloride. Processes 1a and 1b, 2 and 3bare carried out at a reaction temperature between 0°-130° C, at normalpressure, and in solvents or diluents.

Examples of suitable solvents or diluents are: ether and etherealcompounds, such as diethyl ether, dipropyl ether, dioxan,tetrahydrofuran; amides, such as N,N-dialkylated carboxylic amides;aliphatic, aromatic, and halogenated hydrocarbons, in particularbenzene, toluene, xylenes, chloroform, chlorobenzene; nitriles, such asacetonitrile; dimethyl sulphoxide; ketones, such as acetone, methylethyl ketone; water.

The starting materials of the formulae II to XI can be manufactured byknown methods analogous to those described, for example, in J. org.Chem. 30'3217 (1965).

The compounds of the formula display a broad biocidal activity and aretherefore suitable for combating various plant and animal pests and foruse as plant growth regulators.

Surprisingly, however, the compounds of the formula possess inparticular insecticidal and acaricidal properties which are superior tothose of known analogous compounds and can be used against alldevelopment stages, e.g. eggs, larvae, pupae, nymphs and adults, ofinsects and representatives of the order Acarina, e.g. against insectsof the families:

    ______________________________________                                        Tettigoniida      Tenebrionidae                                               Gryllidae         Chrysomelidae                                               Gryllotalpidae    Bruchidae                                                   Blattidae         Tineidae                                                    Reduviidae        Noctuidae                                                   Phyrrhocoridae    Lymatriidae                                                 Cimicidae         Pyralidae                                                   Delphacidae       Culicidae                                                   Aphididae         Tipulidae                                                   Diaspididae       Stomoxydae                                                  Pseudococcidae    Trypetidae                                                  Scarabacidae      Muscidae                                                    Dermestidae       Calliphoridae and                                           Coccinellidae     Pulicidae                                                   Lepidoptera                                                                   ______________________________________                                    

Beyond insects and nematodes the new compounds were found unexpectedlyactive against nematodes and fungi.

Acarida of the families:

Ixodidae

Argasidae

Tetranychidae and

Dermanyssidae.

The insecticidal and/or acaricidal action can be substantially broadenedand adapted to suit the particular circumstances by the addition ofother insecticides and/or acaricides.

Organic phosphorus compounds

Bis-O,O-diethylphosphoric acid anhydride (TEPP)

Dimethyl-(2,2,2-trichloro-1-hydroxyethyl)-phosphonate (TRICHLORFON)

1,2-dibromo-2,2-dichloroethyldimethylphosphate (NALED)

2,2-dichlrovinyldimethylphosphate (DICHLORVOS)

2-methoxycarbamyl-1-methylvinyldimethylphosphate (MEVINPHOS)

Dimethyl-1-methyl-2-(methylcarbamyol)-vinylphosphate cis (MONOCROTOPHOS)

3-(dimethoxyphosphinyloxy)-N,N-dimethyl-cis-crotonamide (DICROTOPHOS)

2-chloro-2-diethylcarbamoly-1-methylvinyldimethylphosphate(PHOSPHAMIDON)

O,o-diethyl-O(or S)-2-(ethylthio)-ethylthiophosphate (DEMETON)

S-ethylthioethyl-O,O-dimethyl-dithiophosphate (THIOMETON)

O,o-diethyl-S-ethylmercaptomethyldithiophosphate (PHORATE)O,O-diethyl-S-2-(ethylthio)ethyldithiophosphate (DISULFOTON)

O,o-dimethyl-S-2-(ethylsulphinyl)ethylthiophosphate (OXYDEMETON METHYL)

O,o-dimethyl-S-(1,2-dicarbethoxyethyldithiophosphate (MALATHION)

O,o,o,o-tetraethyl-S,S'-methylene-bis-dithiophosphate (ETHION)

O-ethyl-S,S-dipropyldithiophosphate

O,o-dimethyl-S-(N-methyl-N-formylcarbamoylmethyl)-dithiophosphate(FORMOTHION)

O,o-dimethyl-S-(N-methylcarbamoylmethyl)dithiophosphate (DIMETHOATE)

O,o-dimethyl-O-p-nitrophenylthiophosphate (PARATHION-METHYL)

O,o-diethyl-O-p-nitrophenylthiophosphate (PARATHION)

O-ethyl-O-p-nitrophenylphenylthiophosphate (EPN)

O,o-dimethyl-O-(4-nitro-m-tolyl)thiophosphate (FENITROTHION)

O,o-dimethyl-O-2,4,5-trichlorophenylthiophosphate (RONNEL)

O-ethyl-O,2,4,5-trichlorophenylethylthiophoasphate (TRICHLORONATE)

0,0-dimethyl-0-2,5-dichloro-4-bromophenylthiophosphate (BROMOPHOS)

O,o-dimethyl-O-(2,5-dichloro-4-iodophenyl)-thiophosphate (JODOFENPHOS)

4-tert.butyl-2-chlorophenyl-N-methyl-O-methylamidophosphate (CRUFOMATE)

O,o-dimethyl-O-(3-methyl-4-methylmercaptophenyl)thiophosphate (FENTHION)

Isopropylamino-O-ethyl-O-(4-methylmercapto-3-methylphenyl)phosphate

O,o-diethyl-O-p-(methylsulphinyl)phenyl-thiophosphate (FENSULFOTHION)

O-p-(dimethylsulphamido)phenyl-O,O-dimthylthiophosphate (FAMPHUR)O,O,O',O'-tetramethyl-O,O'-thiodi-p-phenylenethiophosphate

O-ethyl-S-phenyl-ethyldithiophosphate

O,o-dimethyl-O-(α-methylbenzyl-3-hydroxycrotonyl)phosphate

2-chloro-1-(2,4-dichlorophenyl)vinyl-diethylphosphate (CHLORFENVINPHOS)

1-chloro-1-(2,4,5-trichlorophenyl)vinyl-dimethylphosphate

O-[2-chloro-1-(2,5-dichlorophenyl)]vinyl-O,O-diethylthiophosphate

Phenylglyoxylonitriloxime-O,O-diethylthiophosphate (PHOXIM)

O,o-diethyl-O-(3-chloro-4-methyl-2-oxo-2-H-1-benzopyran-7-yl)-thiophosphate(COUMAPHOS)

2,3-p-dioxandithiol-S,S-bis(O,O-diethyldithiophosphate) (DIOXATHION)

5-[(6-chloro-2-oxo-3-benzoxazolinyl)methyl]O,O-diethyldithiophosphate(PHOSALONE)

2-(dieth9xyphosphinylimino)-1,3-dithiolane

O,o-dimethyl-S-[2-methoxy-1,3,4-thiadiazol-5-(4H)-only-(4)-methyl]dithiophosphate

O,o-dimethyl-S-phthalimidomethyl-dithiophosphate (IMIDAN)

O,o-diethyl-O-(3,5,6-trichloro-2-pyridyl)thiophosphate

O,o-diethyl-O-2-pyrazinylthiophosphate (THIONAZIN)

O,o-diethyl-O-(2-isopropyl-4-methyl-6-pyrimidyl)thiophosphate (DIAZINON)

O,o-diethyl-O-(2-quinoxalyl)thiophosphate

O,o-dimethyl-S-(4-oxo-1,2,3-benzotriazin-3(4H)-ylmethyl)dithiophosphate(AZINPHOSMETHYL)

O,o-diethyl-S-(4-oxo-1,2,3-benzotraizin-3-(4H)-ylmethyl)dithiophosphate(AZINPHOSETHYL)

S-[(4,6-diamino-s-traizin-2-yl)methyl]-O,O-dimethyldithiophosphate(MENAZON)

O,o-dimethyl-O-(3-chloro-4-nitrophenyl)thiophosphate (CHLORTHION)

O,o-dimethyl-O(or S)-2-(ethylthioethyl)thiophosphate (DEMETON-S-METHYL)

2-(o,o-dimethyl-phosphoryl-thiomethyl)-5-methoxy-pyrone-4-3,4-dichlorobenzyl-triphenylphosphoniumchloride

O,o-diethyl-S-(2,5-dichlorophenylthiomethyl)dithiophosphate (PHENKAPTON)

O,o-diethyl-O-(4-methyl-cumarinyl-7-)-thiophosphate (POTASAN)

5-amino-bis(dimethylamido)phosphinyl-3-phenyl-1,2,4-triazole(TRIAMIPHOS)

N-methyl-5-(0,0-dimethylthiolphosphoryl)-3-thiavaleramide (VAMIDOTHION)

O,o-dethyl-O-[2-dimethylamino-4-methylpyrimidyl-(6)]-thiophosphate(DIOCTHYL)

O,o-dimethyl-S-(methylcarbamoylmethyl)-thiophosphate (OMETHOATE)

O-ethyl-O-(8-quinolinyl)-phenylthiophosphonate (OXINOTHIOPHOS)

O-methyl-S-methyl-amidothiophosphate (MONITOR)

O-methyl-O-(2,5-dichloro-4-bromophenyl)-benzothiophosphate (PHOSVEL)

O,o,o,o-tetrapropyldithiophosphate

3-(dimethoxyphosphinyloxy)-N-methyl-N-methoxy-cis-crotonamide

O,o-dimethyl-S-(N-ethylcarbamoylmethyl)dithiophosphate (ETHOATE-METHYL)

O,o-diethyl-S-(N-isopropylcarbamoylmethyl)-dithiophosphate (PROTHOATE)

S-n-(1-cyano-1-methylethyl)carbamoylmethyldiethylthiolphosphate(CYANTHOATE)

S-(2-acetamidoethyl)-O,O-dimethyldithiophosphate

Hexamethylphosphoric acid triamide (HEMPA)

O,o-dimethyl-O-(2-chloro-4-nitrophenyl)thiophosphate (DICAPTHON)

O,o-dimethyl-O-p-cyanophenyl thiophosphate (CYANOX)

O-ethyl-O-P-Cyanophenylthiophosphonate

O,o-diethyl-O-2,4-dichlorophenylthiophosphate (DICHLORFENTHION)

O,2,4-dichlorophenyl-O-methylisopropylamidothiophosphate

O,o-diethyl-O-2,5-dichloro-4-bromophenylthiophosphate (BROMOPHOS-ETHYL)

dimethyl-p-(methylthio)phenylphosphate

O,o-dimethyl-O-p-sulphamidophenylthiophosphate

O-[p-(p-chlorophenyl)azophenyl]O,O-dimethylthiophosphate (AZOTHOATE)

O-ethyl-S-4-chlorophenyl-ethyldithiophosphate

O-isobutyl-S-p-chlorophenyl-ethyldithiophosphate

O,o-dimethyl-S-p-chlorophenylthiophosphate

O,o-dimethyl-S-(p-chlorophenylthiomethyl)dithiophosphate

O,o-diethyl-p-chlorophenylmercaptomethyl-dithiophosphate(CARBOPHENOTHION)

O,o-diethyl-S-p-chlorophenylthiomethyl-thiophosphate

O,o-dimethyl-S-(carbethoxy-phenylmethyl)dithiophosphate (PHENTHOATE)

O,o-diethyl-S-(carbofluorethoxy-phenylmethyl)dithiophosphate

O,o-dimethyl-S-carboisopropoxy-phenylmethyl)-dithiophosphate

O,o-diethyl-7-hydroxy-3,4-tetramethylene-coumarinyl-thiophosphate(COUMITHOATE)

2-methoxy-4-H-1,3,2-benzodioxaphosphorin -2-sulphide

O,o-diethyl-O-(5-phenyl-3-isooxazolyl)thiophosphate

2-(diethoxyphosphinylimino)-4-methyl-1,3-dithiolane

tris-(2-methyl-1-aziridinyl)-phosphine oxide (METEPA)

S-(2-chloro-1-phthalimidoethyl)-O,O-diethyldithiophosphate

N-hydroxynaphthalimido-diethylphosphate

dimethyl-3,5,6-trichloro-2-pyridylphosphate

O,o-dimethyl-O-(3,5,6-trichloro-2-pyridyl)thiophosphate

S-2-(ethylsulphonyl)ethyl dimethylthiolphosphate (DIOXYDEMETON-S-METHYL)

diethyl-S-2-(ethylsulphinyl)ethyl dithiophosphate (OXIDISULFOTON)

bis-O,O-diethylthiophosphoric acid anhydride (SULFOTEP)

dimethyl-1,3-di(carbomethoxy)-1-propen-2-yl-phosphate

dimethyl-(2,2,2-trichloro-1-butyroyloxyethyl)phosphate (BUTONATE)

O,o-dimethyl-O-(2,2-dichloro-1-methoxy-vinyl)phosphate

bis-(dimethylamido)fluorphosphate (DIMEFOX)

3,4-dichlorobenzyl-triphenylphosphoniumchloride

dimethyl-N-methoxymethylcarbamoylmethyl-dithiophosphate (FORMOCARBAM)

O,o-diethyl-O-(2,2-dichloro-1-chloroethoxyvinyl)phosphate

O,o-dimethyl-O-(2,2-dichloro-1-chloroethoxyvinyl)phosphate

O-ethyl-S,S-diphenyldithiolphosphate

O-ethyl-S-benzyl-phenyldithiophosphonate

O,o-diethyl-S-benzyl-thiolphosphate

O,o-dimethyl-S-(4-chlorophenylthiomethyl)dithiophosphate(METHYLCARBOPHENOTHION)

O,o-dimethyl-S-(ethylthiomethyl)dithiophosphate

diisopropylaminofluorophosphate (MIPAFOX)

O,o-dimethyl-S-(morpholinylcarbamoylmethyl)dithiophosphate (MORPHOTHION)

bismethylamidio-phenylphosphate

O,o-dimethyl-S-(benzenesulphonyl)dithiophosphate

O,o-dimethyl-(S and O)-ethylsulphinylethylthiophosphate

O,o-diethyl-O-4-nitrophenylphosphate

triethoxy-isopropoxy-bis(thiophosphinyl)disulphide

2-methoxy-4H-1,3,2-benzodioxaphosphorin-2-oxide

octamethylpyrophosphoramide (SCHRADAN)

bis-(dimethoxythiophosphinylsulphido)-phenylmethane

N,n,n',n'-tetramethyldiamidofluorophosphate (DIMEFOX)

O-phenyl-O-p-nitrophenyl-methanethiophosphonate (COLEP)

O-methyl-O-(2-chloro-4-tert.butyl-phenyl)-N-methylamidothiophosphate(NARLENE)

O-ethyl-O-(2,4-dichlorophenyl)-phenylthiophosphonate

O,o-diethyl-O-(4-methylmercapto-3,5-dimethylphenyl)-thiophosphate

4,4'-bis-(O,O-dimethylthiophosphoryloxy)-diphenyl disulphide

O,o-di-(β-chloroethyl)-O-(3-chloro-4-methyl-coumarinyl-7)-phosphate

S-(1-phthalimidoethyl)-O,O-diethyldithiophosphate

O,o-dimethyl-O-(3-chloro-4-diethylsulphamylphenyl)-thiophosphate

O-methyl-O-(2-carbisopropoxyphenyl)-amidothiophosphate

5-(O,O-dimethylphosphoryl)-6-chloro-bicyclo(3.2.0)-heptadiene(1,5)

O-methyl-O-(2-i-propoxycarbonyl-1-methylvinyl)-ethylamidothiophosphate.

Nitrophenols and derivatives

4,6-dinitro-6-methylphenol, sodium salt [Dinitrocresol]

dinitrobutylphenol-(2,2',2")-triethanolamine salt

2-cyclohexyl-4,6-dinitrophenyl [Dinex]

2-(1-methylheptyl)-4,6-dinitrophenyl-crotonate [Dinocap]

2-sec.-butyl-4,6-dinitrophenyl-3-methyl-butenoate [Binapacryl]

2-sec.-butyl-4,6-dinitrophenyl-cyclopropionate

2-sec.-butyl-4,6-dinitrophenylisopropylcarbonate [Dinobuton]

Miscellaneous

pyrethin I

pyrethin II

3-allyl-2-methyl-4-oxo-2-cyclopentan-1-yl-chrysanthemumate (Allethrin)

6-chloropiperonyl-chrysanthemumate (Barthrin)

2,4-dimethylbenzyl-chrysanthemumate (Dimethrin)

2,3,4,5-tetrahydrophthalimidomethylchrysanthemumate

4-chlorobenzyl-4-chlorophenylsulphide [Chlorobensid]

6-methyl-2-oxo-1,3-dithiolo-[4,5-b]-quinoxaline (Quinomethionate)

(I)-3-(2-furfuryl)-2-methyl-4-oxocyclopent-2-enyl(I)-(cis+trans)chrysanthemum-monocarboxylate[Furethrin]

2-pivaloyl-indane-1,3-dione [Pindon]

N'-(4-chloro-2-methylphenyl)-N,N-dimethylformamidine [Chlorophenamidin]

4-chlorobenzyl-4- fluorophenyl-sulphide [Fluorobenside]

5,6-dichloro-1-phenoxycarbamyl-2-trifluoromethyl-benzimidazole[Fenozaflor]

p-chlorophenyl-p-chlorobenzenesulphonate [Ovex]

p-chlorophenyl-benzenesulphonate [Fenson]

p-chlorophenyl-2,4,5-trichlorophenylsulphone [Tetradifon]

p-chlorophenyl-2,4,5-trichlorophenylsulphide [Tetrasul]

p-chlorobenzyl-p-chlorophenylsulphide [Chlorobenside]

2-thio-1,3-dithiolo-(5,6)-quinoxaline [Thiochinox]

prop-2-ynyl-(4-t-butylphenoxy)-cyclohexylsulphite [Propargil].

Formamidines

1-dimethyl-2-(2'-methyl-4'-chlorophenyl)-formamidine (CHLORPHENAMIDIN)

1-methyl-2-(2'-methyl-4'-chlorophenyl)-formamidine

1-methyl-2-(2'-methyl-4'-bromophenyl)-formamidine

1-methyl-2-(2',4'-dimethylphenyl)-formamidine

1-n-butyl-1-methyl-2-(2'-methyl-4'-chlorophenyl)-formamidine

1-methyl-1-(2'-methyl-4'-chloroaniline-methylene)-formamidine

2-(2"-methyl-4"-chlorophenyl-formamidine

1-n-butyl-2-(2'-methyl-4'-chlorophenyl-imino)-pyrolidine.

Urea

N-2-methyl-4-chlorophenyl-N',N'-dimethyl-thiourea.

Carbamates

1-naphthyl-N-methylcarbamate (CARBARYL)

2-butinyl-4-chlorophenylcarbamate

4-dimethylamino-3,5-xylyl-N-methylcarbamate

4-dimethylamino-3-tolyl-N-methylcarbamate (AMINOCARB)

4-methylthio-3,5-xylyl-N-methylcarbamate (METHIOCARB)

3,4,5-trimethylphenyl-N-methylcarbamate

2-chlorophenyl-N-methylcarbamate (CPMC)

5-chloro-6-oxo-2-norborane-carbonitrile-O-(methylcarbamoyl)-oxime

1-(dimethylcarbamoyl)-5-methyl-3-pyrazolyl-N,N-dimethylcarbamate(DIMETILAN)

2,3-dihydro-2,2-dimethyl-7-benzofuranyl-N-methylcarbamate (CARBOFURAN)

2-methyl-2-methylthio-propionaldehyde-O-(methylcarbamoyl)-oxime(ALDICARB)

8-quinaldyl-N-methylcarbamate and its salts

methyl-2-isopropyl-4-(methylcarbamoyloxy)carbanilate

m-(1-ethylpropyl)phenyl-N-methylcarbamate

3,5-di-tert.butyl-N-methylcarbamate

m-(1-methylbutyl)phenyl-N-methylcarbamate

2-isopropylphenyl-N-methylcarbamate

2-sec.butylphenyl-N-methylcarbamate

m-tolyl-N-methylcarbamate

2,3-xylyl-N-methylcarbamate

3-isopropylphenyl-N-methylcarbamate

3-tert.butylphenyl-N-methylcarbamate

3-sec.butylphenyl-N-methylcarbamate

3-isopropyl-5-methylphenyl-N-methylcarbamate (PROMECARB)

3,5-diisopropylphenyl-N-methylcarbamate

2-chloro-5-isopropylphenyl-N-methylcarbamate

2-chloro-4,5-dimethylphenyl-N-methylcarbamate

2-(1,3-dioxolan-2-yl)phenyl-N-methylcarbamate (DIOXACARB)

2-(4,5-dimethyl-1,3-dioxolan-2-yl)phenyl-N-methylcarbamate2-(1,3-dioxolan-2-yl)phenyl-N,N-dimethylcarbamate

2-(1,3dithiolan-2-yl)-N,N-dimethylcarbamate

2-(1,3-dithiolan-2-yl)phenyl-N,N-dimethylcarbamate

2-isopropoxyphenyl-N-methylcarbamate (APROCARB)

2-(2-propinyloxy)-phenyl-N-methylcarbamate

3-(2-propinyloxy)phenyl-N-methylcarbamate

2-dimethylaminophenyl-N-methylcarbamate

2-diallylaminophenyl-N-methylcarbamate

4-diallylamino-3,5-xylyl-N-methylcarbamate (ALLYXICARB)

4-benzothienyl-N-methylcarbamate

2,3-dihydro-2-methyl-7-benzofuranyl-N-methylcarbamate

3-methyl-1-phenylpyrazol-5-yl-N,N-dimethylcarbamate

1-isopropyl-3-methylpyrazol-5-yl-N,N-dimethylcarbamate (ISOLAN)

2-dimethylamino-5,6-dimethylpyrimidin-4-yl-N,N-dimethyl-carbamate

3-methyl-4-dimthylaminomethyleneiminophenyl-N-methylcarbamate

3,4-dimethylphenyl-N-methylcarbamate

2-cyclopentylphenyl-N-methylcarbamate

3-dimethylamino-methyleneiminophenyl-N-methylcarbamate (FORMETANATE) andits salts

1-methylthio-ethylimino-N-methylcarbamate (METHOMYL)

2-methylcarbamoyloximino-1,3-dithiolane

5-methyl-2-methylcarbamoyloximino-1,3-oxythiolane

2-(1-methoxy-2-propoxy)phenyl-N-methylcarbamate

2-(1-butin-3-yl-oxy)phenyl-N-methylcarbamate

1-dimethylcarbamyl-1-methylthio-O-methylcarbamyl-formoxime

1-(2'-cyanoethylthio)-O-methylcarbamyl-acetaldoxime

1-methylthio-O-carbamyl-acetaldoxime

O-(3-sec.butylphenyl)-N-phenylthio-N-methylcarbamate

2,5-dimethyl-1,3-dithiolane-2-(O-methylcarbamyl)-aldoxime)

O-2-diphenyl-N-methylcarbamate

2-(N-methylcarbamyl-oximino)-3-chloro-bicyclo[2.2.1]heptane

2-(N-methylcarbamyl-oximino)-bicyclo[2.2.1]heptane

3-isopropylphenyl-N-methyl-N-chloroacetal-carbamate

3-isopropylphenyl-N-methyl-N-methylthiomethyl-carbamate

O-(2,2-dimethyl-4-chloro-2,3-dihydro-7-benzofuranyl)-N-methylcarbamate

O-(2,2,4-trimethyl-2,3-dihydro-7-benzofuranyl)-N-methylcarbamate

O-naphthyl-N-methyl-acetal-carbamate

O-5,6,7,8-tetrahydronaphthyl-N-methyl-carbamate

3-isopropyl-4-methylthio-phenyl-N-methylcarbamate

3,5-dimethyl-4-methoxy-phenyl-N-methylcarbamate

3-methoxymethoxy-phenyl-N-methylcarbamate

3-allyloxyhenyl-N-methylcarbamate

2-propargyloxymethoxy-phenyl-N-methyl-carbamate

2-allyloxyphenyl-N-methyl-carbamate

4-methoxycarbonylamino-3-isopropylphenyl-N-methyl-carbamate

3,5-dimethyl-4-methoxycarbonylamino-phenyl-N-methyl-carbamate

2-γ-methylthiopropylphenyl-N-methyl-carbamate

3-(α-methoxymethyl-2-propenyl)-phenyl-N-methyl-carbamate

2-chloro-5-tert.-butyl-phenyl-N-methyl-carbamate

4-(methyl-propargylamino-3,5-xylyl-N-methyl-carbamate

4-(methyl-γ-chloroallylamino)-3,5-xylyl-N-methyl-carbamate

4-(methyl-β-chloroallylamino)-3,5-xylyl-N-methyl-carbamate

1-(β-ethoxycarbonylethyl)-3-methyl-5-pyrazolyl-N,N-dimethylcarbamate

3-methyl-4-(dimethylamino-methylmercapto-methyleneimino)phenyl-N-methylcarbamate

1,3-bis(carbamoylthio)-2-(N,N-dimethylamino)-propanehydrochloride

5,5-dimethylhydroresorcinoldimethylcarbamate

2-[ethyl-propargylamino]-phenyl-N-methylcarbamate

2-[methyl-propargylamino]-phenyl-N-methylcarbamate

4-[dipropargylamino]-3-tolyl-N-methylcarbamate

4-[dipropargylamino]-3,5-xylyl-N-methylcarbamate

2-[allyl-isopropylamino]-phenyl-N-methylcarbamate

3-[allyl-isopropylamino]-phenyl-N-methylcarbamate

Chlorinated Hydrocarbons

γ-hexachlorocyclohexane [GAMMEXANE; LINDAN; γHCH]

1,2,4,5,6,7,8,8-octachloro-3α,4,7,7α'tetrahydro-4,7-methylene indane[CHLORDAN]

1,4,5,6,7,8,8-heptachloro,3α,4,7,7α-tetrahydro-4,7-methylene indane[HEPTACHLOR]

1,2,3,4,10,10-hexachloro-1,4,4α,5,8,8α-hexahydro-endo-1,4-exo-5,8-dimethanonaphthalene[ALDRIN]

1,2,3,4,10,10-hexachloro-6,7-epoxy-1,4,4α,5,6,7,8,8α-octa-hydro-exo-1,4,endo-5,8-dimethanonaphthalene[DIFLORIN]

1,2,3,4,10,10-hexachloro-5,7-epoxy-1,4,4α,5,6,7,8,8α-octyhydro-endo-endo-5,8-dimethanonaphthalene[ENDRIN]

The active substances of the formula I are also suitable for combatingrepresentatives of the division Thallophyta, e.g. viruses, bacteria andfungi. They thus possess fungicidal properties against phytopathogenicfungi on various cultivated plants, such as cereals, maize, rice,vegetables, ornamental plants, fruit trees, vines, farm products, etc.

With the new active substances it is possible to control or destroyfungi occurring on fruit, blossom, leaves, stems, tubers and roots, andfrom which parts of plants which grow later then also remain free. Theactive substances of the formula I are active in particular againstphytopathogenic fungi belonging to the following classes: oomycetes,Zygomycetes, Ascomycetes, Basidiomycetes, Denteromycetes.

In addition, the new active substances can also be used for treatingseeds, fruit, tubers etc., and protecting them from fungus infections,for example from smut fungi of all kinds, such as Ustilaginales, e.g.Ustilago, Tilletia, Urocystis, Turbicinia and Phoma types.

In addition to the above cited acaricides and insecticides, it is alsopossible to admix the active substances of the formula I with, forexample, bactericides, fungistatic agents, bacteriostatic agents,nematocides and/or e.g. the following fungicides, in order to broadenthe activity spectrum:

dodecylguanidine acetate (DODINE)

pentachloronitrobenzene (QUINTOZENE)

pentachlorophenol (PCP)

2-(1-methyl-n-propyl)-4,6-dinitrophenyl-2-methyl-crotonate (BINAPACRYL)

2-(1-methyl-n-heptyl)-4,6-dinitrophenylcrotonate (DINOCAP)

2,6-dichloro-4-nitroaniline (DICHLORAN)

2,3,5,6-tetrachloro-benzoquinone (1,4) (CHLORANIL)

2,3-dichloro-naphthoquinone (1,4) (DICHLONE)

N-(trichloromethylthio) phthalimide (FLOPAT)

N-(trichloromethylthio) cyclohex-4-ene-1,2-dicarboximide (CAPTAN)

N-(1,1,2,2-tetrachloroethylthio)cyclohex-4-ene-1,2-dicarboximide(CAPTAFOL)

N-methansulfonal-N-trichloromethylthio-chloroaniline

N'-dichlorofluoromethylthio-N,N-dimethyl-N'-phenylsulphamide(DICHLOFLUANID)

O-ethyl-S-benzyl-phenyldithiophosphate

O,o-diethyl-S-benzyl-thiolphosphate

disodium-ethylene-1,2-bis-dithiocarbamate (NABAM)

zinc-ethylene-1,2-bis-dithiocarbamate (ZINEB)

manganese-ethylene-1,2-bis-dithiocarbamate (polymeric) (MANEB)

tetramethylthiuramidsulphide (THIRAM)

1-oxy-3-acetyl-6-methyl-cyclohexene-(5)dione-(2,4) (DEHYDRO-ACETIC ACID)

8-hydroxyquinoline (8-QUINOLINOL)

2-dimethylalimo-6-methyl-5-n-butyl-4-hydroxy-pyrimidine

methyl-N-benzimidazole-2-yl-N-(butylcarbamoyl)carbamate (BENOMYL)

2-ethylamino-6-methyl-5N-butyl-4-hydroxypyrimidine

2,3-dicyano-1,4-dithia-anthraquinone (DITHIANON)

2-(4-thiazolyl)-benzimidazole

3,5-dimethyltetrahydro-1,3,5-thiadiazine-2-thione (DAZOMET)

2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathine pentachlorobenzylalcohol.

Furthermore, the compounds of the formula I are suitable for combatingplant pathogenic nematodes.

The compounds of the formula I may be used as pure active substance ortogether with suitable carriers and/or additives. Suitable carriers andadditives can be solid or liquid and correspond to the substancesconventionally used in formulation technique such, for example, assolvents, dispersants, wetting agents, adhesives, thickeners, bindersand/or fertilisers.

For application, the compounds of the formula I may be processed todusts, emulsion concentrates, granules, dispersions, sprays, tosolutions, or suspensions, in the conventional formulation which iscommonly employed in application technology. Mention may also be made ofcattle dips and spray races, in which aqueous preparations are used.

The agents according to the invention are manufactured in known mannerby intimately mixing and/or grinding active substances of the formula Iwith the suitable carriers, optionally with the addition of dispersantsor solvents which are inert towards the active substances. The activesubstances may take, and be used in, the following forms.

Solid forms

Dusts, tracking agents, granules, coated granules, impregnated granulesand homogeneous granules.

Liquid forms

a. active substances which are dispersible in water: wettable powders,pasts, emulsions;

b. solutions.

To manufacture solid forms (dusts, tracking agents), the activesubstances are mixed with solid carriers. Suitable carriers are, forexample: kaolin, talcum, bolus, loess, chalk, limestone, groundlimestone, attaclay, dolomite, diatomaceous earth, precipitated silica,alkaline earth silicates, sodium and potassium aluminium silicates(feldspar and mica), calcium and magnesium sulphates, magnesium oxide,ground synthetic materials, fertilisers, for example ammonium sulphate,ammonium phosphate, ammonium nitrate, urea, ground vegetable products,such as corn meal, bark dust, sawdust, nutshell meal, cellulose powder,residues of plant extractions, activated charcoal etc. These substancescan either be used singly or in admixture with one another.

Granules can be very easily manufactured by dissolving an activesubstance of the formula I in an organic solvent and applying theresulting solution to a granulated material, for example attapulgite,SiO₂, granicalcium, bentonite etc. and then evaporating the solvent.

Polymer granules can also be manufactured by mixing the activesubstances of the formula I with polymerisable compounds(urea/formaldehyde; dicyandiamide/formaldehyde; melamine/formaldehyde orothers), whereupon a mild polymerisation is carried out that does notaffect the active substances and in the process of which the granulationis carried out during the gel formation. It is more advantageous toimpregnate finished, porous polymer granules (urea/formaldehyde,polyacrylonitrile, polyester or others) which have a specific surfacearea and a favourable predeterminable adsorption/desorption ratio, withthe active substances, for example in the form of their solutions (in alow boiling solvent) and to remove the solvent. Polymer granules of thiskind in the form of microgranules having a bulk density of 300 g/literto 600 g/liter can also be manufactured with the aid of atomisers. Thedusting can be carried out from aircraft over extensive areas ofcultures of useful plants.

It is also possible to obtain granules by compacting the carrier withthe active substance and carriers and subsequently comminuting theproduct.

To these mixtures can also be added additives which stabilise the activesubstance and/or non-ionic, anionic and cationic surface activesubstances, which, for example, improve the adhesion of the activeingredients on plants or parts of plants (adhesives and agglutinants)and/or ensure a better wettability (wetting agents) and dispersibility(dispersing agents). Examples of suitable adhesives are the following:olein/chalk mixture, cellulose derivatives (methyl cellulose,carboxymethyl cellulose), hydroxyethyl glycol ethers of monoalkyl anddialkyl phenols having 5 to 15 ethylene oxide radicals per molecule and8 to 9 carbon atoms in the alkyl radical, ligrain sulphonic acids, theiralkali metal and alkaline earth metal salts, polyethylene glycol ethers(carbowaxes), fatty alcohol polyethylene glycol ethers having 5 to 20ethylene oxide radicals per molecule and 8 to 18 carbon atoms in thefatty alcohol moiety, condensation products of ethylene oxide/ propyleneoxide, polyvinyl pyrrolidones, polyvinyl alcohols, condensation productsof urea and formaldehyde, and also latex products.

The water-dispersible concentrates of the active substance, i.e.wettable powders, pastes and emulsifiable concentrates, are agents whichcan be diluted with water to any concentration desired. They consist ofactive substance, carrier, optionally additives which stabilise theactive substance, surface-active substance and anti-foam agents and,optionally, solvents.

Wettable powders and pastes are obtained by mixing and grinding theactive substances with dispersing agents and pulverulent carriers insuitable apparatus until homogeneity is attained. Suitable carriers are,for example, those mentioned for the solid forms of application. In somecases it is advantageous to use mixtures of different carriers. Asdispersing agents there can be used, for example, condensation productsof sulphonated naphthalene and sulphonated naphthalene derivatives withformaldehyde, condensation products of naphthalene or naphthalenesulphonic acids with phenol and formaldehyde, as well as alkali,ammonium and alkaline earth metal salts of lignin sulphonic acid, inaddition, alkylaryl sulphonates, alkali and alkaline earth metal saltsof dibutyl naphthalene sulphonic acid, fatty alcohol sulphates such assalts of sulphated hexadecanols, heptadecanolo, octadecanols, and saltsof sulphated fatty alcohol glycol ethers, the sodium salt of oleoylethionate, the sodium salts of oleoyl methyl tauride, ditertiaryacetylene glycols, dialkyl dilauryl ammonium chloride and fatty acidalkali and alkaline earth metal salts.

Suitable anti-foam agents are silicones.

The active substances are mixed, ground, sieved and strained with theadditives cited hereinabove in such a manner that, the size of the solidparticles does not exceed 0.02 to 0.04 μ in wettable powders, and 0.03 μin pastes. To produce emulsifiable concentrates and pastes, dispersingagents such as those cited above, organic solvents, and water are used.Examples of suitable solvents are: alcohols, benzene, xylene, toluene,dimethyl sulphoxide, and mineral oil fractions which boil between 120°and 350° C. The solvents must be practically odourless, not phytotoxic,and inert to the active substances.

Furthermore, the agents according to the invention can be applied in theform of solutions. For this purpose the active substances, or severalactive substances of the general formula I, are dissolved in suitableorganic solvents, mixtures of solvents or in water. Aliphatic andaromatic hydrocarbons, chlorinated derivatives thereof, alkylnaphthalenes, and mineral oils, singly or in admixture with each other,can be used as organic solvents.

The content of active substance in the above described agents is between0.1% to 95%, in which connection it should be mentioned that, in thecase of application from aircraft or some other suitable means ofapplication, it is possible to use concentrations of up to 99.5% or evenpure active substance.

The active substances of the formula I can, for examle, be formulated asfollows:

Dusts

The following substances are used to manufacture (a) a 5% and (b) a 2%dust:

a.

5 parts of active substance

95 parts of talcum

b.

2 parts of active substance

1 part of highly disperse silicic acid

97 parts of talcum.

The active substances are mixed with the carriers and ground.

Granules

The following substances are used to produce 5% granules:

≡parts of active substance,

0.25 parts of epichlorohydrin,

0.25 parts of cetyl polyglycol ether,

3.50 parts of polyethylene glycol,

91 parts of kaolin (particle size 0.3 - 0.8 mm).

The active substance is mixed with epichlorohydrin and dissolved with 6parts of acetone; the polyethylene glycol and cetyl polyglycol ether arethen added. The thus obtained solution is sprayed on kaolin, and theacetone subsequently evaporated in vacuo.

Wettable powder

The following constituents are used for the preparation of (a) also a40%, (b) and (c) a 25%, and (d) a 10% wettable powder:

a.

40 parts of active substance,

5 parts of sodium lignin sulphonate,

1 part of sodium dibutyl-naphthalene sulphonate,

54 parts of silicic acid.

b.

25 parts of active substance,

4.5 parts of calcium lignin sulphonate,

1.9 parts of Champagne chalk/hydroxyethyl cellulose mixture (1:1),

1.5 parts of sodium dibutyl naphthalene sulphonate,

19.5 parts of silicic acid,

19.5 parts of Champagne chalk,

28.1 parts of kaolin.

c.

25 parts of active substance,

2.5 parts of isooctylphenoxy-polyoxyethylene-ethanol,

1.7 parts of Champagne chalk/hydroxyethyl cellulose mixture (1:1),

8.3 parts of sodium aluminum silicate,

16.5 parts of kieselguhr,

46 parts of kaolin.

d.

10 parts of active substance,

3 parts of a mixture of the sodium salts of saturated fatty alcoholsulphates,

5 parts of naphthalenesulphonic acid/formaldehyde condensate,

82 parts of kaolin.

The active substances are intimately mixed, in suitable mixers, with theadditives, the mixture being then ground in the appropriate mills androllers. Wettable powders are obtained which can be diluted with waterto give suspensions of any desired concentration.

Emulsifiable concentrates

The following substances are used to produce (a) a 10% and (b) a 25%emulsifiable concentrate:

a.

10 parts of active substance,

3.4 parts of epoxidised vegetable oil,

13.4 parts of a combination emulsifier consisting of fatty alcoholpolyglycol ether and alkylarylsulphonate calcium salt,

40 parts of dimethylformamide,

43.2 parts of xylene.

b.

25 parts of active substance,

2.5 parts of epoxidised vegetable oil,

10 parts of an alkylarlysulphonate/fatty alcohol-polyglycol ethermixture

5 parts of dimethylformamide,

57.5 parts of xylene.

From these concentrates it is possible to produce, by dilution withwater, emulsions of any desired concentration.

Spray

The following constituents are used to prepare a 5% spray:

5 parts of active substance,

1 part of epichlorohydrin,

94 parts of benzine (boiling limits 160° - 190° C).

EXAMPLE 1 O-ethyl-S-n-propyl-O-(3-nitrophenyl)-thiophosphoric ester

To a solution of 18.1 g of m-nitrophenol in 150 ml of benzene are added13.3 g of triethylamine. While stirring constantly, 26.4 g ofO-ethyl-S-n-propylchlorothiolphosphoric ester are added dropwise at10°-15° C. The reaction mixture is stirred for 12 hours, then washedwith water, 3% Na₂ CO₃ solution and again with water, and dried oversodium sulphate. The benzene is distilled off. Molecular distillation ofthe residue at 135° C/0.001 Torr yields the compound of the formula##STR5## The following compounds are also manufactured in analogousmanner: ##STR6##

    ______________________________________                                        R.sub.1  R.sub.2       R'         Physical Data                               ______________________________________                                        C.sub.2 H.sub.5                                                                     C.sub.3 H.sub.7(n)                                                                                        n.sub.D 25: 1,5374                          C.sub.2 H.sub.5                                                                     C.sub.4 H.sub.9(n)                                                                         n.sub.D 25: 1,5272                                         C.sub.2 H.sub.5                                                                     C.sub.4 H.sub.9(n)                                                                         n.sub.D 25: 1,5263                                         C.sub.2 H.sub.5                                                                     C.sub.3 H.sub.7(n)                                                      C.sub.2 H.sub.5     ##STR9##                                                        C.sub.3 H.sub.7(n)                                                                         n.sub.D 25: 1,5233                                         C.sub.2 H.sub.5                                                                     C.sub.3 H.sub.7(n)                                                      C.sub.2 H.sub.5     ##STR11##                                                       C.sub.3 H.sub.7(n)                                                                         n.sub.D 25: 1,5366                                         C.sub.2 H.sub.5                                                                      AB,4 C.sub.3 H.sub.7(n)                                                                   n.sub.D 25: 1,5442                                         C.sub.2 H.sub.5                                                                     C.sub.3 H.sub.7(n)                                                                         n.sub.D 23: 1,5409                                         C.sub.2 H.sub.5                                                                     C.sub.3 H.sub.7(n)                                                      C.sub.2 H.sub.5     ##STR15##                                                       CH.sub.2 CH(CH.sub.3).sub.2                                             C.sub.2 H.sub.5     ##STR16##                                                       CH.sub.2 CH(CH.sub.3).sub.2                                             C.sub.2 H.sub.5     ##STR17##                                                       CH.sub.2 CH(CH.sub.3).sub.2                                                                 ##STR18##                                                 ______________________________________                                    

EXAMPLE 2 O-Ethyl S-1O'-4-Nitrophenyl Thiophosphate

O,O-Diethyl-O-4-nitrophenyl thiophosphate (58.2 g., 0.2 mole) and 22.4g. (0.2 mole) of triethylenediamine were left to stir at ambienttemperature for 24 hours. The resulting, viscuous liquid was dissolvedin 500 me. of acetonitrile and 49.2 g. (0.4 mole) of 1-bromo propanewere added. The reaction mixture was heated to 70° C for 2 hours andworked up to give 25.2 g. of 82% pure product which was foundsurprisingly effective against fungi, specifically against bean rust.

Anal. Calcd. for C₁₁ H₁₆ O₅ PS: C, 43.41; H, 5.25; P, 10.16; Found: C,43.03; H, 5.38; P, 10.01.

EXAMPLE 3 A. Insecticidal ingest poison action

Tobacco and potato plants were sprayed with a 0.05% aqueous emulsion(obtained from a 10% emulsifiable concentrate).

After the coating had dried, the tobacco plants were populated withEgyptian cotton leaf worms (Spodoptera littoralis) and the potato plantswith Colorado potato beetle larvae (Leptinotarsa decemlineata). The testwas carried out at 24° C and 60% relative humidity. In the above testthe compounds according to Example 1 displayed ingest poison actionagainst Spodoptera littoralis and Leptinotarsa decemlineata.

B. Systemic insecticidal action

To determine the systemic action, rooted bean plants (Vicia fabae) wereput into a 0.01% aqueous active substance solution (obtained from a 10%emulsifiable concentrate). After 24 hours, aphids (Aphis fabae) wereplaced on the parts of the plant above the soil. The aphids wereprotected from contact and gas action by means of a special device. Thetest was carried out at 24° C and 70% relative humidity. In the abovetests the compounds according to Example I displayed insecticidal ingestposion action and systemic insecticidal action.

EXAMPLE 4 Action against Chilo suppressalis

Six rice plants at a time of the variety Caloro were transplanted intoplastic pots (diameter at the top= 17 cm) and reared to a height ofabout 60 cm. Infestation with Chilo suppressalis larvae (L₁ :3-4 mmlong) took place 2 days after the active substance had been applied ingranule form to the paddy water (rate of application: 8 kg of activesubstance per hectare). Evaluation of the insecticidal action ensued 10days after application of the granules.

The compounds according to Example I were active in the above testagainst Chilo suppressalis.

EXAMPLE 5 Action against soil insects

Sterilised compost earth was homogeneously mixed with a wettable powdercontaining 25% of active substance so as to produce a rate ofapplication of 8 kg of active substance per hectare.

Young zuccetti plants (Cucumis pepo)were put into plastic pots with thetreated soil (3 plants per pot; diameter of pot = 7 cm). Each pot wasinfected immediately afterwards with 5 Aulacophora femoralis andPachmoda or Chortophila larvae. The control was carried out 4, 8, 16 and32 days after the larvae had been put into the soil.

At 80-100% kill after the first control, a fresh infestation with 5larvae per pot was carried out in the same soil sample with 3 newzucchetti plants. If the activity was less than 80%, the remaininglarvae remained in the soil sample until the control immediatelyfollowing. If an active substance at a rate of application of 8 kg/hastill effected a 100% kill, a further control with 4 and 2 kg of activesubstance per hectare was carried out.

In the above test, the compounds according to Example I displayed actionagainst Aulacophora fermoralis, Pachmoda and Chortophila larvae.

EXAMPLE 6 Action against ticks A. Rhicephalus bursa

Five adult ticks or 50 tick larvae were counted into a test tube andimmersed for 1 to 2 minutes in 2 ml of an aqueous emulsion from anemulsion series each containing 100, 10, 1 and 0.1 ppm of testsubstance. The tube was the sealed with a standardised cotton wool plugand stood on its head so as to enable the cotton wool to absorb theactive substance emulsion.

In the case of the adults evaluation took place after 2 weeks, and inthat of the larvae after 2 days. Each test was repeated twice.

B. Boophilus microplus (larvae)

Tests were carried out with 20 sensitive and 20 OPresistent larvae witha dilution series analogous to that used in test A. (The resistencerefers to the tolerability of Diazinon).

In these tests the compounds according to Example 1 acted against adultsand larvae of Rhipicephalus bursa and sensitive and OP-resistent larvaeof Boophilus microplus.

EXAMPLE 7 Acaracidal action

Phaseolus vulgaris (dwarf beans) were overlaid with a piece of leaf froma mass culture of Tetranychus urticae 12 hours before the test for theacaricidal action. The mobile stages which had spread over the plantswere sprayed with the emulsified test preparations from a chromatographyatomiser so that the spray broth did not run off. The number of livingand dead larvae, adults and eggs were evaluated after 2 to 7 days undera steroscopic microscope and the result was expressed in percentages.During the "interim", the treated plants were kept in greenhousecompartments at 25° C.

The compounds according to Example I acted in the above test againsteggs, larvae and adults of Tetranychus urticae.

EXAMPLE 8 Action against soil nematodes

To test the action against soil nematodes, the active substances wereapplied to, and intimately mixed with soil infected with root gallnematodes (Meloidgyne arenaria) in the specifically indicatedconcentrations. Immediately afterwards, tomato cuttings were planted inthe thus prepared soil in a series of tests and after a waiting time of8 days tomato seeds were sown in another test series.

In order to assess the nematocidal action, the galls present on theroots were counted 28 days after planting and sowing respectively. Thecompounds according to Example I to 4 displayed good action in this testagainst Meloidgyne arenaria.

We claim:
 1. The compound of the formula ##STR19##
 2. The compound ofthe formula